AADE-04-DF-HO-30

Shale Analysis for Mud Engineers

D. Breeden, J. Shipman, OGS Laboratory Inc.

This paper was prepared for presentation at the AADE 2004 Drilling Fluids Conference, at the Radisson Astrodome in Houston, Texas, April 6-7, 2004. This conference was sponsored by the Houston
Chapter of the American Association of Drilling Engineers. The information presented in this paper does not reflect any position, claim or endorsement made or implied by the American Association of
Drilling Engineers, their officers or members. Questions concerning the content of this paper should be directed to the individuals listed as author/s of this work.

Abstract To begin, a simplified explanation of the basic theory

In the process of drilling oil and gas wells an of XRD will be given. Hopefully, this will provide the
interaction occurs between the drilling fluid and the readers with enough information that they may be able
formations drilled. A simple analysis of the formation to determine if XRD is useful for the applications they
composition can help understand the problems and are interested in, and suggest other information that may
successes using a particular fluid in different fields. An be useful.
understanding of what comprises a formation can lead to
better formulation of the drilling fluid. XRD - Determining crystal structure
One of the methods used to identify the basic In essence, the diffractogram produced by XRD
mineralogy of a formation is X-Ray Diffraction (XRD). permits understanding of the arrangement of the atoms
XRD determines the crystalline structure of the minerals in a material. Each mineral has a unique arrangement of
being tested by determining the angles at which the X- atoms, referred to as its crystal structure or lattice, and
Ray beam is diffracted. This results in a pattern that is these atoms are arranged in infinite repeating planes.
unique to a particular mineral. Analysis of the patterns Depending on the distance between these planes, the x-
from a formation sample can help identify the minerals rays will diffract at a series of specific angles that
present and semi-quantify them. provides a pattern that is explicit for the mineral in
An oriented clay slide is prepared and a series of question; see Figure 1. This can be used as a
chemical and physical manipulations of the slide are fingerprint for that mineral.
conducted. XRD is used to observe the changes at each As suggested in Figure 2 the sample is placed
step to identify the basic clay minerals present and can between a source of x-rays and an x-ray detector. By
provide an estimate of their relative concentration. changing the angle of the sample holder, relative to the
The cation exchange capacity (CEC) of clays is a source, each crystal plane gets an opportunity to diffract
method used to determine the reactivity of a clay and its respective angle of x-rays. The detector identifies
thus the shale. Additional information about the which angles produce its respective reflected x-ray.
reactivity of the shale can be obtained, if the For example, quartzs major plane has a d-spacing of
exchangeable cations are identified and quantified. 3.44 . Applying this to an equation called Braggs Law
(n = 2d sin) the diffraction angle 2 can be predicted to
be about 26.6o. Looking at Figure 3 one can see a large
Introduction peak at 26.62o with an intensity of 6299 counts per
Understanding the minerals that make-up a particular second (cps).
material is vital in many industries. In the oil industry, The other peaks in the diffractogram are associated
specifically, understanding the constituents of a with other crystal planes and are important in verifying
geological formation under investigation can have that the mineral is actually present (i.e. the rest of its
implications as to what site is chosen for drilling. Once a unique fingerprint).
site has been chosen this mineralogical information can
be used to anticipate certain expectations about the field Clays Discussion
due to the minerals revealed. This leads to further It is hard to distinguish the clays from each other in
implications, such as the customization of drilling fluids XRD due to the fact that their structure and d-spacings
for the site. As minerals are crystalline the use of x-ray are similar to one another. However, the species can be
diffraction (XRD) to identify and determine the distinguished by exposing the clays to chemical or
approximate amount of each species is used. physical changes. Chemicals consisting of water and
The objective of this paper is to help the reader better ethylene glycol may be inserted, naturally or artificially,
understand the procedure that OGS Laboratory Inc. between the lattice planes. This will cause the lattice
(OGS) performs when a shale sample is submitted from spacing to alter and thus it will change the position and
the field. This will, in turn, enable the reader to better appearance of the diffraction peak. The application of
interpret the XRD analysis reports given out by OGS and heat has two effects. Heat expels the aforementioned
other laboratories. chemicals therefore altering the crystal planes again.
Alternatively, applying heat can result in a variety of
2 D. Breeden, J. Shipman
instabilities of the crystal within itself. The lattice will
have to compensate for these instabilities by changing
its d-spacing and, thus, altering the diffraction peaks.
Methods
Sample preparation
The method used is derived from the method
3
described by Schultz. The sample is washed using a
variety of organic liquids and solvents. After this the
sample is dried and hand ground so that it passes
through a fine sieve. The powder is then ground
mechanically for 15 minutes to achieve optimum grain
size.
Bulk analysis
This entails looking at a broad range of potential
angles of diffraction for the sample. Therefore the x-ray
diffractometer is set to scan the sample starting at angle
3.5o and ending at 70.0o at a constant speed. This
allows the technician to see any possible minerals in the
sample. It is vitally important that the powders
orientation be as random as possible so that each
mineral gets a fair representation of itself. A further
discussion of this topic will be given later.
By using a spreadsheet and a programmed macro
the computer mathematically generates the results for
the minerals listed in Table 1. See Figure 4 for an
example of what is obtained when doing a bulk analysis.
If other high intensity peaks appear that are not
associated with the minerals listed in Table 1 it is up to
the technician doing the analysis to identify those peaks
manually. The amounts of these extra minerals may be
approximated depending on the mineral. Some of the
more common ones are listed in Table 2.
Oriented Clay Slides
About 2 grams of the powdered sample is mixed with
30mL of deionized water. This is stirred and then
allowed to stand so that the more dense particles sink
and the clay particles remain suspended in the upper
layer of water. A pipette is used to extract this clay
solution and deposit it on to a frosted glass slide. The
water is allowed to evaporate overnight; this is done
because, in this case, the particles on the slide need to
be oriented.
The individual clays (kaolinite, illite, smectite and
chlorite) are distinguished by the clay slide. For each
run the range of 2 of interest is 3.5o-20o. The clay slide
is manipulated and then scanned using XRD after each
step of the process.
The clay slide will be scanned four times. First, the
slide is run in the diffractometer after all the water has
evaporated. This initial run is referred to as the fines
sample, it can be thought of as the before snap-shot of
the manipulations. The slide is then put in a desiccator
with ethylene glycol in it and heated to 70oC. (A spare
desiccator is ideal for this because it allows the pool of
AADE-04-DF-HO-30
glycol to sit at the bottom and be partitioned from the
slide resting on a screen above the glycol.) After about
2 hours the slide is briefly air dried and analyzed on the
diffractometer again. This diffractogram is referred to as
the glycolated sample. The slide is then put in an oven
at 300oC for about an hour and a half. After cooling to
room temperature, the diffraction peaks are obtained
and this data is labeled 300oC. Similarly, the oven is
heated to 550oC and the slide is heated at this
temperature for about 30-minutes. On cooling, the slide
is run again, and this data is labeled 550oC. The
glycolation process, alone, distinguishes the clay
smectite. The mixed-layer of illite and smectite is
determined by the combined manipulations of glycolation
and heating to 300oC. Kaolinite is determined by
heating to 300oC. Chlorite is noted by its dramatic lattice
collapse after heating to 550oC. Illite is distinguished by
its ability to resist all of these manipulations.3 As with
the bulk analysis a macro is performed on the collected
data according to some calculations briefly discussed
below.
Semi-quantifying using Microsoft Excel
Using a Microsoft Excel macro, the data, obtained by
the XRD software, is processed for interpretation. A
chart of the minerals commonly found in shales and their
respective primary 2 values are listed in Tables 1 and
2. The pure standards of the minerals in Table 1 are
analyzed in the same manner as the bulk samples.
Here the highest intensity value is noted for all of the
pure standards, see Figures 7-13. This value is used to
semi-quantitate the relative amount of each mineral in
the mixture. By taking the value at that 2 reading in the
sample and dividing that by the value derived from the
pure standard a good estimate of its percentage is given.
For example, refer back to Figure 3 where the quartz
peak has a maximum at 6299 cps. A sample is run and
gives a value of 1417 cps at 26.65o. Therefore the
estimated quartz percentage is 1417/6299=22.5%.
Quartz, feldspar, calcite, dolomite and siderite are
treated in this direct manner. The clays (as a whole) and
pyrite are mathematically manipulated more by factoring
in an intensity factor.
Using a computer macro that compares the
diffractogram of each step the clays are classified and
semi-quantified. Standards are utilized but only for
identification purposes, see Figures 14-17. An example
of the final x-ray analysis process, including bulks and
fines, is given in Figure 5. By looking at each graph from
bottom to top one can see how the peaks alter after
each application of the process. Based on these
changing peaks the computer calculates the final
volumetric percentages. Both the bulk and fines data is
directly interpreted into weight percents because the
densities of the minerals are about the same or because
an intensity factor is used.
AADE-04-DF-HO-30 Shale Analysis for Mud Engineers
Discussions
General Procedures
When a sample is brought to the facility a series of
considerations need to be taken into account. A Patience is a key component in retaining desirable
washing strategy is determined by what needs to be
cleaned off of the sample. A sample may be divided
into several aliquots, and then washed differently to
ensure that if any one of the samples components gets
leeched out in one washing that it will be present in
another. Each washing is analyzed by means of the
XRD procedure discussed above. Heterogeneous
samples maybe compensated for by separating out the
unlike particles into the same number of different
samples and running them accordingly. The weights of
the separated samples are measured so that a
percentage of each can be quantitated. The freshly
washed samples are then dried at about 250oC to make
sure all of the solvents are removed from the sample.
After the grinding process the bulk sample is
prepared for analysis by positioning it on a sample
holder. The technician uses a specialized tool to
assemble this. This tool ensures that the surface of the
sample is ideal for analysis in two ways. In order for the
samples and standards to be compared correctly their
surfaces must be at the same height within the sample
holder each time. Conventionally, this is chosen to be
level with respect to the sample holder. See Figure 6 for
an illustration of this.
The device also allows for ideal packing of the
sample. This is vital because the mineral grains vary in
size and density. If the sample is packed too loosely the
particles will organize themselves in a heterogeneous
fashion. This will cause the surface to be erroneous with
respect to the sample in question. To extrapolate from
this, it is also mentionable that the original powder must
be mixed very well before extracting the powder out to
be analyzed. Due to the fact that mineral grains can
organize themselves almost instantaneously, the
technician must also be careful to extract the sample by
scooping out the contents by touching the bottom of the
container. These techniques, together, will ensure an
acceptable randomized bulk sample that is
representative of the original cuttings.
Ideally, when the bulk powder is mixed into the water
the clays will suspend and the slide will be made
accordingly. Often, a suspension is not produced. This
can arise due to the presence of a water-soluble mineral,
like halite or gypsum. This will dissolve in the water and
prohibit the suspension of the clays. The sample must
then be washed with water extensively until the clays
can be suspended.
In reference to the clay slide itself, it needs to be
emphasized that allowing the water to evaporate as
slowly as possible renders the most desirable results.
When the slide is dried in a heated environment the clay
grains do not become as oriented as they do when it is
allowed to dry overnight at room temperature.
3
Ensuring that the clay layer on the slide is not too
thick or thin is important as well. If the clay is too thick
the sample may peel during heating. If the sample is too
thin the clay-peaks are minimized or absent all together.
results from the clay slides. To add to the making of the
slide each step involves heating the sample for a
particular length of time. The technician must also allow
time for the samples to cool slowly at each step so that
the samples will not bubble and peel (this is similar to
being too thick). Similar to the bulk analysis, the
individual clay slide must be analyzed in the same spot.
The technician simply chooses which end of the slide is
placed into the diffractometer first and consistently uses
that same end.
Limitations
As this is a semi-quantitative computation, emphasis
needs to be placed on the fact that this is a general
approximation of the contents in the sample. XRD, in
general, is ideal for identifying crystalline material.
However, the size of the peak is directly proportional to
the number of lattice planes presented. Therefore the
intensity of the peak is directly related to the percent
volume of the species (being related to the number of
planes diffracted). A limitation to this results from the
shape factor. On grinding the sample into fine particles,
the different minerals within the sample adopt different
shapes. Quartz takes on a spherical shape during
grinding; most other minerals grind to prismatic or
rhombic fragments. Clays tend to produce flakes. The
spherical quartz grains are randomly orientated and so
their peak height is a fair representation of its volumetric
abundance. When a sample is put in a sample holder,
the non-spherical grains have preferred orientation.
Therefore the plane of choice for each of these minerals
may either over-represent or under-represent its
abundance. These limitations do not seem to be too
much of a hindrance due to the needed applications.
Also, this phenomenon is likely to also apply to the
standards so errors are reduced.
Another limitation to keep in mind is that the
standards used in obtaining the pure reading may not
be interpreted correctly. As shown in Figures 7-17 when
applying the pure standards to the macro erroneous
minerals can result. This can result from the extra
mineral actually being in the standard. Alternatively, a
peak from another lattice plane of that standard may be
misinterpreted as a peak from another type of mineral.
In the case of the clay standards erroneous peaks
usually indicate foreign minerals are, indeed, present in
the standard. The best example is shown in Figure 17
where the chlorite standard contains a lot of kaolinite.
(Scattering Electron Microscopy (SEM) has verified the
presence of kaolinite in this standard.) Since the clays
are calculated differently this causes very little concern.
But, in the case of calculating the total clays in the bulk
sample, if a minerals peak under-represents its amount
4 D. Breeden, J. Shipman
the leftover amount is placed in the total clay cell.
This, also, can be seen in the pure non-clay standards,
Figures 7-13. Again, it is up to the technologist to
ensure that the XRD data is interpreted correctly.
Mineral implications in the field
By using the preparation and interpretation
techniques discussed above the expectations of that
field can be predicted. A brief account is given on the
general understanding of how each mineral yields an
idea of what to expect and thus leads to modifying
drilling fluids for the site.
Quartz and the feldspars are crucial to understand
because, together, they are the most abundant minerals
encountered during drilling. Quartz is very hard
(hardness of 7) and abrasive. Its crystals can increase
the porosity of the shale, allowing fluid to penetrate
farther and faster than in similar low quartz shales. This
circumstance can destabilize the shale, leading to
difficulties in drilling. Likewise, feldspars are hard (6
6.5) and are the primary matrix of shales. In other
words, the shale will be more easily dispersed if the
feldspar content is low. Furthermore, the carbonates
(calcite, dolomite and siderite) are of interest because
like quartz they may cause additional porosity to the
shale, but are significantly softer (3 - 4). Some of the
carbonates are also a potential source of low-level
carbonate build-up in the mud. Similarly, pyrite is a hard
mineral (6 6.5) that may impart some increased
porosity to the shale.
Beidellite and montmorillonite are known to be the
most common and most well known smectites,
respectively. It is generally accepted that vermiculites
belong in a separate class from smectite due to differing
CEC results (discussed below). As a group, vermiculites
are much more reactive than the smectites. The
smectite concentration in shale is important. Being that
smectites swell when hydrated, they can make the
formation unstable. Smectite clays are most often
controlled these days with inhibitive water-based, oil, or
synthetic-based fluids. Furthermore, kaolinite is a
dispersive, non-swelling clay. It is commonly found in
drilling wells in the North Sea and off the West Coast of
Africa. Kaolinite can be controlled most effectively with
the addition of a source of potassium. Which leads to
illite, which is a dispersive, non-swelling clay that can
also be controlled by the addition of a source of
potassium or some of the amine compounds, currently in
use today. Similarly, chlorite clays are dispersive, non-
swelling materials that are generally not found in
sufficient quantities to need special attention. Typically,
methods to control the kaolinitic and illitic clays will
generally control the chlorite clays. Mixed layer clays
can be of several types: kaolin/smectite,
chlorite/smectite, chlorite/vermiculite and illite/smectite.
The most frequently found and therefore most important
of these is the illite/smectite mixed layer. When water
interacts with this mixed layer the consequences
AADE-04-DF-HO-30
rendered are much more damaging than if it were pure
smectite or illite. The illite allows the smectite to swell
more easily due to increased exposed surface area.
Also, the mixed layer sets up a situation where the less
reactive clays act like ball bearings for the swelling clays
to roll upon. Macroscopically, this results in
disintegrating shale.
Cation Exchange Capacity (CEC)
CEC values are important due to the fact that clays
vary in their reactivity. Some of the cations (positively
charged atoms) of the clay are easily replaced with other
positively charged species. This phenomenon is driven
by the fact that the original cations are not as compatible
to the negatively charged site as the newly introduced
positively charged species. Thus, it is rationalized that
the exchangeability of the cations are directly related to
the reactivity of the shale. However, the CEC within
itself does not provide this information alone. The
individual cations of the clays that are replaced and left
in solution indicate reactivity of the clay as well. These
cations, also called exchangeable bases, primarily are
calcium, potassium, magnesium, and sodium. For
example, shale with a high CEC value along with a high
concentration of calcium may not be as reactive as shale
with a lower CEC value and a high sodium
concentration.
To summarize the reaction, the Mg2+, Ca2+, K+, and/or
+
Na initially present in the clay are loosely bonded to
negatively charged sites within the clay. The CEC
reagent is a positively charged species in solution. The
clay and the CEC reagent are allowed to mix with one
another for an extended period of time. During this time,
the CEC reagent is strongly attracted to the negatively
charged sites. It is, therefore, drawn out of solution and
bonded to these sites. This in turn, drives the Mg2+,
Ca2+, K+, and/or Na+ into solution. Either Ion
chromatography (IC) or Atomic Absorption Spectroscopy
(AA) can quantify these cations.
OGS has used several CEC procedures.
Methylenblue (MBT) is desirable for the field due to its
fast results. However, it is known that MBT is not very
reliable when compared to the other methods.
Ammonium acetate is commonly used in deriving soil
CEC values for agricultural applications. This procedure
is indeed useful but has limitations. It consists of a
lengthy amount of time to complete. This method is
regarded as an indirect method, which involves a
distillation and titration to derive the CEC value. These
can be easily mishandled and/or misinterpreted which
will lead to inaccurate CEC values. The ammonium left
over from the process is not easily taken out of the
solution and therefore interferes with the calculation of
the cations, if IC is used to identify the cations. This
particular reagent replaces salt and carbonate cations as
well. This can increase the CEC value and render
inaccurate cation counts.
AADE-04-DF-HO-30 Shale Analysis for Mud Engineers
OGS has found the cobalt(III)hexamine procedure to
be very useful.4 It does not demand as much time as
the ammonium acetate procedure. The CEC value is
obtained directly by measuring the cobalt(III)hexamine
concentration by either AA or by UV/Visible
spectrophotometery. See Figure 18 for the complete
XRD and CEC spreadsheet.
In the limited time OGS has been using the cobalt
procedure, we have found that it gives a higher CEC
than does the ammonium procedure. The
corresponding cations also increase an equal amount.
CEC data can indicate whether a clay mineral,
particularly smectite, has a predisposition to cation
retention or whether or not diffusion of charged or
uncharged molecules can occur within the clay.5 In other
words, if a shale has a high CEC it might be able to be
altered either by nature or by the application of a drilling
fluid. This may be detrimental or useful to the drilling
process depending on the alteration.
Conclusions
With good organization skills an accurate account as
to what is included in a sample can be rendered. Being
able to wash and grind a sample effectively is of up-most
importance. Preparing the powdered bulk sample to be
even and as random as possible is vital to the success
of semi-quantitating the minerals. Patience is a
necessity in preparing and manipulating the clay slides
to obtain accurate results. Utilizing CEC to better
understand these minerals is of utmost importance as
well. Having experienced and knowledgeable personnel
executing the procedures is important to ensure that the
best possible analytes are created and that the XRD and
CEC data is interpreted logically. Understanding the
essential theories and applications behind XRD and
CEC will enable the reader to better recognize and
understand these very useful applications. It also
enables the individuals from the field to better interpret
and appreciate the reports submitted by OGS Laboratory
Inc. These factors in combination will, hopefully, provide
the field personnel a better understanding of the site that
they are considering or drilling.
5
References
1. Skoog, D. A., Holler, F. J., Nieman, T. A. Principles of
Instrumental Analysis, 5th Ed.; Saunders College
Publishing: Austin, 1998; 849.
2. West A. R. Basic Solid State Chemistry, 2nd Ed.; John
Wiley & Sons, Ltd: New York, 1999; 480.
3. Schultz L. G. Quantitative interpretation of
mineralogical composition from x-ray and chemical data
for the Pierre Shale, U. S. Geological Survey
professional paper 391-C, 1964.
4. Ciesielski H, Sterckeman T. Determination of cation
exchange capacity and exchangeable cations in soils by
means of cobalt hexamine trichloride. Effects of
experimental conditions, Agronomie (1997) 17, 1-7
5. Meier, L. P., Kahr, G. Determination of the Cation
Exchange Capacity of clay minerals based on the
Complexes of the Copper (II) ion with
Triethylenetetramine and Tetraethylenepentamine,
Clays and Clay Minerals, Vol. 47 No. 3, 386-388, 1999.
Additional Reading
1. Moore, M. M., Reynolds R. C. X-Ray Diffraction and
the Identification of Clay Minerals, 2nd Ed.; Oxford: New
York, 1997; 378.
2. Cullity, B. D. Elements of X-Ray Diffraction; Addison-
Wesley Publishing Co., Inc.: Reading, 1956; 514.

Acknowledgments
A special word of thanks to Dr. James K. Meen, Task
Leader of the Materials Characterization Facility at the
Texas Center of Superconductivity and Applied Materials
of the University of Houston, for his advise.

Nomenclature
AA = Atomic Absorption Spectroscopy
CEC = Cation Exchange Capacity
cps = counts per second
IC = Ion Chromatography
MBT = Methylenblue Test
SEM = Scattering Electron Microscope
XRD = X-Ray Diffraction
6 D. Breeden, J. Shipman AADE-04-DF-HO-30

Table 1
Primary shale minerals and their 2 values

Mineral 2 (degrees)
Quartz 26.6
Feldspar 27.5
Calcite 29.6
Dolomite 31.0
Siderite 31.8
Pyrite 33.1
Clays 19.9
34.6
61.9

Table 2
Additional minerals common in drilling and their 2 Values

Mineral 2 (degrees)
Halite 31.7
Barite 28.9
Portlandite 34.0
Gypsum 11.7
Magnetite 35.5

Figure 1
Simplified Diagram of the diffraction of x-rays by a crystal
(Adapted from ref 1)

Figure 2
Symbolic Schematic of XRD Experiment
(Adapted from ref 2)
AADE-04-DF-HO-30 Shale Analysis for Mud Engineers 7
Figure 3
XRD of pure quartz
8000 Bulk

6000
4000
2000
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Figure 4
Results after a bulk analysis
X-Ray Diffraction Interpretation and Data

Project: NDFH 1978 Sample: 4/11/2003

2000 Bulk

1500
1000
500
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

Quartz 24
Feldspar 3
Calcite 1
Dolomite 2
Siderite 3
Pyrite 0
Total Clay 67
8 D. Breeden, J. Shipman AADE-04-DF-HO-30
Figure 5
Example of Bulks and Fines
X-Ray Diffraction Interpretation and Data

Project: NDFH 1978 Sample: 4/11/2003

2000 Bulk

1500
1000
500
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

900 Fines Fines Quartz 24
Glycolated
Feldspar 3
300C
800 550C
Calcite 1
Dolomite 2
Siderite 3
700
Pyrite 0
Total Clay 67
600
Clay Composition - wt%
500 Kaolinite 23
Chlorite 7
Illite 31
400
Smectite 12
Mixed-layer 28
300 Illite/smectite 25 / 75

200

100

0
0 5 10 15 20 25
Degrees 2 Theta
AADE-04-DF-HO-30 Shale Analysis for Mud Engineers 9
Figure 6

Left to right: Correct and Incorrect way bulk sample should be in sample holder

Figure 7
Quartz Standard
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data

Project: Quartz Sample: Quartz

12000 Bulk
10000
8000
6000
4000
2000
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

Quartz 96
Feldspar 0
Calcite 0
Dolomite 0
Siderite 0
Pyrite 0
Total Clay 4
10 D. Breeden, J. Shipman AADE-04-DF-HO-30
Figure 8
Calcite Standard
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data

Project: Calcite Sample: Calcite Standard

15000 Bulk

10000

5000

0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

Quartz 0
Feldspar 0
Calcite 92
Dolomite 0
Siderite 1
Pyrite 0
Total Clay 8

Figure 9
Standard of Dolomite

X-Ray Diffraction Interpretation and Data

Project: STANDARD Sample: DOLOMITE

Description:

15000 Bulk

10000
5000
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

Quartz 0
Feldspar 1
Calcite 1
Dolomite 87
Siderite 2
Pyrite 1
Total Clay 8
AADE-04-DF-HO-30 Shale Analysis for Mud Engineers 11
Figure 10
Microcline Feldspar Standard
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data

Project: Microcline Sample: Microcline Feldspar

10000 Bulk
8000
6000
4000
2000
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

Quartz 4
Feldspar 66
Calcite 4
Dolomite 4
Siderite 0
Pyrite 0
Total Clay 21

Figure 11
Oligoclase Feldspar
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data

Project: Oligoclase Sample: Oligoclase Feldspar

10000 Bulk
8000
6000
4000
2000
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

Quartz 4
Feldspar 71
Calcite 4
Dolomite 2
Siderite 6
Pyrite 0
Total Clay 14
12 D. Breeden, J. Shipman AADE-04-DF-HO-30
Figure 12
Standard of Pyrite
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data
Project: Pyrite Standard Sample: Pyrite
2500 Bulk
2000
1500
1000
500
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

Quartz 17
Feldspar 1
Calcite 1
Dolomite 1
Siderite 0
Pyrite 77
Total Clay 3

Figure 13
Standard of Siderite
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data
Project: Siderite Standard Sample: Siderite

6000 Bulk
5000
4000
3000
2000
1000
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

Quartz 2
Feldspar 4
Calcite 9
Dolomite 14
Siderite 65
Pyrite 1
Total Clay 6
AADE-04-DF-HO-30 Shale Analysis for Mud Engineers 13
Figure 14
Standard of Smectite
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data

Project: Montmorillonite Sample: Sodium Montmorillonite

1500 Bulk

1000

500

0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

6000 Fines Fines
Glycolated Quartz 3
300C Feldspar 1
550C Calcite 2
5000
Dolomite 0
Siderite 0
Pyrite 0
4000 Total Clay 94

Clay Composition - wt%

3000
Kaolinite 2
Chlorite 4
Illite 7
2000 Smectite 85
Mixed-layer 2
Illite/smectite 5 / 95
1000

0
0 5 10 15 20 25
Degrees 2 Theta
14 D. Breeden, J. Shipman AADE-04-DF-HO-30
Figure 15
Standard of Kaolinite
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data

Project: Kaolin Sample: Fisher Kaolin Standard

5000 Bulk
4000
3000
2000
1000
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

10000 Fines Fines
Glycolated Quartz 5
300C
9000
550C
Feldspar 2
Calcite 1
8000 Dolomite 0
Siderite 1
7000 Pyrite 0
Total Clay 91
6000
Clay Composition - wt%
5000
Kaolinite 79
4000 Chlorite 0
Illite 12
Smectite 0
3000
Mixed-layer 8
Illite/smectite 40 / 60
2000

1000

0
0 5 10 15 20 25
Degrees 2 Theta
AADE-04-DF-HO-30 Shale Analysis for Mud Engineers 15
Figure 16
Standard of Illite
OGS Laboratory, Inc. - X-Ray Diffraction Interpretation and Data

Project: Illite Sample: Illite

3000 Bulk
2500
2000
1500
1000
500
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

1600 Fines Fines
Glycolated Quartz 20
300C
Feldspar 2
1400 550C
Calcite 2
Dolomite 1
1200 Siderite 2
Pyrite 10
Total Clay 63
1000
Clay Composition - wt%
800
Kaolinite 8
Chlorite 3
600 Illite 56
Smectite 4
Mixed-layer 29
400
Illite/smectite 35 / 65

200

0
0 5 10 15 20 25
Degrees 2 Theta
16 D. Breeden, J. Shipman AADE-04-DF-HO-30
Figure 17
Standard of Chlorite
X-Ray Diffraction Interpretation and Data

Project: Chlorite Std Sample: 1/16/04

Description: Chlinochlore

4000 Bulk

3000
2000
1000
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

1400 Fines Fines
Quartz 2
Glycolated Feldspar 1
300C Calcite 2
1200 550C Dolomite 1
Siderite 0
Pyrite 0
1000 Total Clay 93

Clay Composition - wt%

800 Kaolinite 45
Chlorite 17
Illite 19
600 Smectite 18
Mixed-layer 0
Illite/smectite 20 / 80
400

200

0
0 5 10 15 20 25
Degrees 2 Theta
AADE-04-DF-HO-30 Shale Analysis for Mud Engineers 17

Figure 18
Complete Report: XRD & CEC
X-Ray Diffraction Interpretation and Data

Project: NDFH 1978 Sample: 4/11/2003

2000 Bulk

1500
1000
500
0
0 10 20 30 40 50 60 70 80
Degrees 2 Theta

Bulk Composition - wt%

900 Fines Fines Quartz 24
Glycolated
Feldspar 3
300C
800 550C
Calcite 1
Dolomite 2
Siderite 3
700
Pyrite 0
Total Clay 67
600
Clay Composition - wt%
500 Kaolinite 23
Chlorite 7
Illite 31
400
Smectite 12
Mixed-layer 28
300 Illite/smectite 25 / 75

200 CEC - meq/100 g

13.1
100

Exchangeable Bases - meq/100 g

0 Potassium 2.6
0 5 10 15 20 25 Magnesium 0.5
Degrees 2 Theta Sodium 2.2
Calcium 10.8